CA2013305A1 - Process for preparing polyketones - Google Patents
Process for preparing polyketonesInfo
- Publication number
- CA2013305A1 CA2013305A1 CA002013305A CA2013305A CA2013305A1 CA 2013305 A1 CA2013305 A1 CA 2013305A1 CA 002013305 A CA002013305 A CA 002013305A CA 2013305 A CA2013305 A CA 2013305A CA 2013305 A1 CA2013305 A1 CA 2013305A1
- Authority
- CA
- Canada
- Prior art keywords
- formula
- anion
- ethylene
- acid
- palladium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
- C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated compounds
Abstract
Case 7178(2) ABSTRACT OF THE DISCLOSURE
PROCESS FOR PREPARING POLYKETONES
An improved process for preparing linear interpolymers of olefin(s) (eg ethylene) and carbon monoxide (Polyketones) is provided. The process comprises polymerising the olefin(s) with carbon monoxide in the presence of a palladuim catalyst derived from a palladuim source, a bidentate amine, phosphine, arsine or stibine of formula (R1)2M -R2 -M(R1)2 where the M atoms are selected from N, P, As or Sb, the R1 groups are eg C1 to C4 alkyl or phenyl and R2 is eg -(CH2)-a where a - 2 to 10, and a anion prepared by reacting in a 2:1 molar ratio and substituted salicylic acid and boric acid. The salicylic acid is preferably 4- or 5- substituted with methyl, C1 or Br. Using this particular palladuim catalyst leads to high polymer yields than eg when unsubstituted salicylic acid is employed.
PROCESS FOR PREPARING POLYKETONES
An improved process for preparing linear interpolymers of olefin(s) (eg ethylene) and carbon monoxide (Polyketones) is provided. The process comprises polymerising the olefin(s) with carbon monoxide in the presence of a palladuim catalyst derived from a palladuim source, a bidentate amine, phosphine, arsine or stibine of formula (R1)2M -R2 -M(R1)2 where the M atoms are selected from N, P, As or Sb, the R1 groups are eg C1 to C4 alkyl or phenyl and R2 is eg -(CH2)-a where a - 2 to 10, and a anion prepared by reacting in a 2:1 molar ratio and substituted salicylic acid and boric acid. The salicylic acid is preferably 4- or 5- substituted with methyl, C1 or Br. Using this particular palladuim catalyst leads to high polymer yields than eg when unsubstituted salicylic acid is employed.
Description
Case 7178(2) PROCESS FOR PREPARING POLYKETONES
The present invention relates to a process for preparing interpolymers of olefins and carbon monoxide by polymerising a mixture of one or more olefins and carbon monoxide in the presence of a palladium catalyst. In particular, the present invention relates to new palladium catalysts for use in such processes.
The preparation of linear interpolymers of olefins and carbon monoxide having the formula:
o [ (CR2~CR2)nC]m where the R groups are independently hydrogen or hydrocarbyl groups, n is at least 1 and m is a large integer, is known from US 3694412.
Such linsar interpolymers, which hereaftar will be called polyketones, are prepared according to US 3694412 by polymerising a mixture of one or more olefins and carbon monoxide in the presence of an aryl phosphine complex of a palladium halide and an inert solvent. However, the processes described in US 3694412 arP slow even at elevated temperature and pressure.
An improved version of the process described in US 3694412 is describad in European patent applications 101014 and 121965. It was found that the rate of the polymerisation process could be increased considerably by using a palladium catalyst with inter alia a bidentate phosphine and the anion of a ~arboxylic acid having a pKa of lower than 2 (as measured in aqueous solution). Examples of anions which can be used include trichloroacetate, dichloroacetate, tetrafluoroborate, hexafluorophosphate and p-toluene sulphonate, ~ ~ ? 5 7 ~? J
such anions being respectively the conjugate anions of trichloroacetic acid (pKa 0.70), dichloroacetic acid (pKa = 1.48), tetrafluoroboric acid, hexafluorophosphoric acid and p-toluenesulphonic acid.
Nore recently EP 222454 suggests that any acid having a pKa of less than 5 (determined in agueous solution at 18C) can be used.
Our recent European patent application discloses that if anions of certain boron containing acids, which anions have formulae such as: o o Il il ~ \ - / ~ or ~ CO ~ _ / C
are used instead of the anions disclosed in either EP 181014 or 222454, then particularly high reaction rates can be achieved.
Furthermore, if such anions are employed, lower catalyst deactivation on recycle is observed relative to previously described systems.
Whilst good reaction rates can be achieved using such anions, it is clearly desirable if possible to secure a further increase in reaction rates. The problem to be solved is therefore to improve the rate of polyketone production obtained using a catalyst system comprising a palladium catalyst, a bidentate phosphine or the like and an anion.
~ccordingly, the present inventions provides a process for preparing polyketones by polymerising a mixture of carbon monoxide and one or more olefins in the presence of a palladium catalyst characterised in that the palladium catalyst is prepared by reac-ting together:
(a) a source of palladium, (b) a bidentate amine, phosphine, arsine or stibine having the formula (Rl)2M-R2-M(Rl)2 wherein the M atoms are independently selected from nitrogen, phosphorus, arsenic or antimony, the Rl are independently alkyl, cycloalkyl or aryl groups and R2 is an alkylene group, and (c) a source of an anion having the formula:
, 3 ~ ~J
Rl O, Rl R2X~ CO~ ~OC~, R2 wherein Rl, R2, R3 and R4 are independently selected from the group consisting of hydrogen, Cl to C6 alkyl, chlorine, bromine and iodine with the proviso that at least one of ~l, R2, R3 and R4 is other than hydrogen.
The present invsntion solves the problem by using certain selected anions of boron containing acids. Their use leads to an increase yield of polyketone in a given period of time The anion employed in the process of the present invention is one having the formula given above in which Rl, R2, R3 and R4 are independently selected from hydrogen, Cl to C6 alkyl, chlorine, bromine and iodine. This is subject to the proviso that at least one of these groups are other than hydrogen. Preferred derivatives are those where one of Rl, R2, R3 and R4 is selected from the Cl to C4 alkyl, chlorine and bromine with the other three groups being hydrogen. Nost preferred are those anions prepared by reacting l mole of boric acid with 2 moles of an acid selected from 5-chlorosalicyclic acid, 5- or 4-methylsalicyclic acid and 5-bromosalicyclic acid.
The palladium catalyst used in the process described above is itself prepared by reacting together a source of palladium, an appropriate amine, phosphine, arsine or stibine and anion having the formula defined above. S~ch a catalyst can be prepared beforehand or generated in situ under the process conditions. As regards the source of palladiu~ thls can include simple inorganic and organic salts, e.g. halides, nitrates, carboxylates and the like as well as organometallic and coordination complexes.
Although any source of palladium can be used, it may be necessary, when a palladium complax having strongly coordinating ligands is employed, to ensure that such ligand~ are removed prior to reaction with the other catalyst components. An example of such ~J~J ~
a complex is palladium acetat~ where acetate anions bind strongly to the palladium. In this case the acetate anions can be removed by adding catalyst component (c) above as its conjugate acid since this will protonate the acetate anions and cause their removal.
Another approach, which is useful when palladium halides are employed (halide anions also bind strongly to the palladium), is to use a thallium or silver salt of catalyst component (c). In this case a metathesis reaction occurs and insoluble silver or thallium halide precipitates which can be removed by filtration.
The other component of the catalyst i8 a bidentate amine, phosphine, arsine or stibine having the formula (Rl)2M-R2-M(Rl)2 where the M atoms are independently selected from nitrogen, phosphorus, arsenic or antimony. The Rl groups are independently selected from alkyl, cycloalkyl or aryl groups with Cl to C4 alkyl and phenyl groups being preferred. The R2 group is an alkylene group. In the context of this document alkylene groups are defined as being -(CH2)a(CHR3)b- groups in which the R3 groups are independently hydrogen, methyl, ethyl or propyl groups and a and b are either zero or integers such that a+b is at least 2, preferably between 2 and 10. Preferably the alkylene group is selected from -(CH2)2-~ -(CH2)3-~ -(CH2)4- and -(CH2)s-. Of these the most convenient species are the bidentate phosphines, 1,2-bis(dipheDylphosphino)ethane (dipho~), 1,3-bis(diphenylphosphino)propane and 1,4-bis(diphenylphosphino) butane.
The bidentate amines, phosphines, arsines or stibines defined above all either bond exclusively cis to the palladium or tbere is a reasonable concentration of this cis binding. Whilst no~ wishing to be held to any theory, it is believed that it is the cis type isomer of the palladium complex which is catalytically active.
Considering next the feedstocks for the polymarisatlon feedstoGk, it is believed that any reasonably pure source of carbon monoxide can be used. Thus the carbon monoxide may contain small amounts of nitrogen, inert gases and up to 10% hydrogen.
Any olefin can in theory be used although the best reaction f,',,~ p.
rates are obtained when Cl to Clo alpha-olefins especially when either ethylene or a mixture of olefins which include ethylene, e.g. ethylene/propylene, ethylene/butylene and the like, are used.
The lower rates obtained in the absence of ethylene should not however be construed as indicating that the process can be used only with an ethylene feedstock since other olefins such as propylene, 4-methylpentene-1, styrene, acrylates, vinyl acetates and the like all undergo reaction to some extent.
The polymerisation procPss is suitably carried out in a solvent which is chemically inert under the conditions employed and one in which the palladium catalyst is soluble. Moreover, the solvent like the anion should be either weakly or non-coordinating. Examples of such solvents include alcohols, e.g. methanol, ethanol and propanol, ethers, glycols and glycol ethers. Preferred solvents are methanol or ethoxyethanol.
The polymerisation process is suitably carried out at a temperature in the range 20 to 150C and at elevated pressure, (e.g. 1 to 100 bars). The overpressure of gas is suitably supplied by the carbon monoxide or carbon monoxide and the olefin, if the olefin is gaseous under the reaction conditions. It is possible to operate the polymerisation process either batchwise or continuously.
The following Examples illustrate the present invention.
Example 1 - Com~arative Exam~le usin~ the anion of BorosalicYlic acid A stainless steel autoclavo of 150 ml capacity was charged with palladium acetate (25 mg), 1.3-bis~diphenylphosphino)propane (66 mg), boro~alicylic acid (HBSA) (600 mg), methanol (39 cm3) and a magnetic stirrer bar. The autoclave was flushed with nitrogen, charged with ethylene (20 bar) and thereafter carbon monoxide (30 bar), and heated to 100C. After 0.7 hours gas uptake had virtually ceased and a pressure drop of 29.0 bar had been recorded.
The vessel was allowed to cool over a period of 1~ hours, and was vented at 30C. The polymer was recovered by filtration, washed with methanol, then acetone and air dried at room temperature.
4.62g of polymer was recovered.
5--3 1 ~"; P~
Examples 2-5 Use of Anions accordin~ to the Invention The method of Example 1, except that HBSA was replaced with a mixture of the relevant substituted salicyclic acid and boric acid (2:1 molar). The results are recorded in Table 1.
Table 1 ~xample Salicyclic Wt of Wt Oe - Time Wt of Acid SAD Boric Acid bar h Polymer Derivative mg mg g . .. _ . .. ___ 2 5-Chloro 690.3 122.8 32.6 0.46 6.41 3 5-Methyl 608.9 123.0 24.7 0.36 5.89 4 4-Methyl 607.9 123.4 25.7 0.48 5.05 5-Bromo 868.7 122.8 30.5 0.80 S.27 Examples 2-5 clearly show the improved yields of polymer obtained relative to the prior art material exemplified by Example 1. --~0
The present invention relates to a process for preparing interpolymers of olefins and carbon monoxide by polymerising a mixture of one or more olefins and carbon monoxide in the presence of a palladium catalyst. In particular, the present invention relates to new palladium catalysts for use in such processes.
The preparation of linear interpolymers of olefins and carbon monoxide having the formula:
o [ (CR2~CR2)nC]m where the R groups are independently hydrogen or hydrocarbyl groups, n is at least 1 and m is a large integer, is known from US 3694412.
Such linsar interpolymers, which hereaftar will be called polyketones, are prepared according to US 3694412 by polymerising a mixture of one or more olefins and carbon monoxide in the presence of an aryl phosphine complex of a palladium halide and an inert solvent. However, the processes described in US 3694412 arP slow even at elevated temperature and pressure.
An improved version of the process described in US 3694412 is describad in European patent applications 101014 and 121965. It was found that the rate of the polymerisation process could be increased considerably by using a palladium catalyst with inter alia a bidentate phosphine and the anion of a ~arboxylic acid having a pKa of lower than 2 (as measured in aqueous solution). Examples of anions which can be used include trichloroacetate, dichloroacetate, tetrafluoroborate, hexafluorophosphate and p-toluene sulphonate, ~ ~ ? 5 7 ~? J
such anions being respectively the conjugate anions of trichloroacetic acid (pKa 0.70), dichloroacetic acid (pKa = 1.48), tetrafluoroboric acid, hexafluorophosphoric acid and p-toluenesulphonic acid.
Nore recently EP 222454 suggests that any acid having a pKa of less than 5 (determined in agueous solution at 18C) can be used.
Our recent European patent application discloses that if anions of certain boron containing acids, which anions have formulae such as: o o Il il ~ \ - / ~ or ~ CO ~ _ / C
are used instead of the anions disclosed in either EP 181014 or 222454, then particularly high reaction rates can be achieved.
Furthermore, if such anions are employed, lower catalyst deactivation on recycle is observed relative to previously described systems.
Whilst good reaction rates can be achieved using such anions, it is clearly desirable if possible to secure a further increase in reaction rates. The problem to be solved is therefore to improve the rate of polyketone production obtained using a catalyst system comprising a palladium catalyst, a bidentate phosphine or the like and an anion.
~ccordingly, the present inventions provides a process for preparing polyketones by polymerising a mixture of carbon monoxide and one or more olefins in the presence of a palladium catalyst characterised in that the palladium catalyst is prepared by reac-ting together:
(a) a source of palladium, (b) a bidentate amine, phosphine, arsine or stibine having the formula (Rl)2M-R2-M(Rl)2 wherein the M atoms are independently selected from nitrogen, phosphorus, arsenic or antimony, the Rl are independently alkyl, cycloalkyl or aryl groups and R2 is an alkylene group, and (c) a source of an anion having the formula:
, 3 ~ ~J
Rl O, Rl R2X~ CO~ ~OC~, R2 wherein Rl, R2, R3 and R4 are independently selected from the group consisting of hydrogen, Cl to C6 alkyl, chlorine, bromine and iodine with the proviso that at least one of ~l, R2, R3 and R4 is other than hydrogen.
The present invsntion solves the problem by using certain selected anions of boron containing acids. Their use leads to an increase yield of polyketone in a given period of time The anion employed in the process of the present invention is one having the formula given above in which Rl, R2, R3 and R4 are independently selected from hydrogen, Cl to C6 alkyl, chlorine, bromine and iodine. This is subject to the proviso that at least one of these groups are other than hydrogen. Preferred derivatives are those where one of Rl, R2, R3 and R4 is selected from the Cl to C4 alkyl, chlorine and bromine with the other three groups being hydrogen. Nost preferred are those anions prepared by reacting l mole of boric acid with 2 moles of an acid selected from 5-chlorosalicyclic acid, 5- or 4-methylsalicyclic acid and 5-bromosalicyclic acid.
The palladium catalyst used in the process described above is itself prepared by reacting together a source of palladium, an appropriate amine, phosphine, arsine or stibine and anion having the formula defined above. S~ch a catalyst can be prepared beforehand or generated in situ under the process conditions. As regards the source of palladiu~ thls can include simple inorganic and organic salts, e.g. halides, nitrates, carboxylates and the like as well as organometallic and coordination complexes.
Although any source of palladium can be used, it may be necessary, when a palladium complax having strongly coordinating ligands is employed, to ensure that such ligand~ are removed prior to reaction with the other catalyst components. An example of such ~J~J ~
a complex is palladium acetat~ where acetate anions bind strongly to the palladium. In this case the acetate anions can be removed by adding catalyst component (c) above as its conjugate acid since this will protonate the acetate anions and cause their removal.
Another approach, which is useful when palladium halides are employed (halide anions also bind strongly to the palladium), is to use a thallium or silver salt of catalyst component (c). In this case a metathesis reaction occurs and insoluble silver or thallium halide precipitates which can be removed by filtration.
The other component of the catalyst i8 a bidentate amine, phosphine, arsine or stibine having the formula (Rl)2M-R2-M(Rl)2 where the M atoms are independently selected from nitrogen, phosphorus, arsenic or antimony. The Rl groups are independently selected from alkyl, cycloalkyl or aryl groups with Cl to C4 alkyl and phenyl groups being preferred. The R2 group is an alkylene group. In the context of this document alkylene groups are defined as being -(CH2)a(CHR3)b- groups in which the R3 groups are independently hydrogen, methyl, ethyl or propyl groups and a and b are either zero or integers such that a+b is at least 2, preferably between 2 and 10. Preferably the alkylene group is selected from -(CH2)2-~ -(CH2)3-~ -(CH2)4- and -(CH2)s-. Of these the most convenient species are the bidentate phosphines, 1,2-bis(dipheDylphosphino)ethane (dipho~), 1,3-bis(diphenylphosphino)propane and 1,4-bis(diphenylphosphino) butane.
The bidentate amines, phosphines, arsines or stibines defined above all either bond exclusively cis to the palladium or tbere is a reasonable concentration of this cis binding. Whilst no~ wishing to be held to any theory, it is believed that it is the cis type isomer of the palladium complex which is catalytically active.
Considering next the feedstocks for the polymarisatlon feedstoGk, it is believed that any reasonably pure source of carbon monoxide can be used. Thus the carbon monoxide may contain small amounts of nitrogen, inert gases and up to 10% hydrogen.
Any olefin can in theory be used although the best reaction f,',,~ p.
rates are obtained when Cl to Clo alpha-olefins especially when either ethylene or a mixture of olefins which include ethylene, e.g. ethylene/propylene, ethylene/butylene and the like, are used.
The lower rates obtained in the absence of ethylene should not however be construed as indicating that the process can be used only with an ethylene feedstock since other olefins such as propylene, 4-methylpentene-1, styrene, acrylates, vinyl acetates and the like all undergo reaction to some extent.
The polymerisation procPss is suitably carried out in a solvent which is chemically inert under the conditions employed and one in which the palladium catalyst is soluble. Moreover, the solvent like the anion should be either weakly or non-coordinating. Examples of such solvents include alcohols, e.g. methanol, ethanol and propanol, ethers, glycols and glycol ethers. Preferred solvents are methanol or ethoxyethanol.
The polymerisation process is suitably carried out at a temperature in the range 20 to 150C and at elevated pressure, (e.g. 1 to 100 bars). The overpressure of gas is suitably supplied by the carbon monoxide or carbon monoxide and the olefin, if the olefin is gaseous under the reaction conditions. It is possible to operate the polymerisation process either batchwise or continuously.
The following Examples illustrate the present invention.
Example 1 - Com~arative Exam~le usin~ the anion of BorosalicYlic acid A stainless steel autoclavo of 150 ml capacity was charged with palladium acetate (25 mg), 1.3-bis~diphenylphosphino)propane (66 mg), boro~alicylic acid (HBSA) (600 mg), methanol (39 cm3) and a magnetic stirrer bar. The autoclave was flushed with nitrogen, charged with ethylene (20 bar) and thereafter carbon monoxide (30 bar), and heated to 100C. After 0.7 hours gas uptake had virtually ceased and a pressure drop of 29.0 bar had been recorded.
The vessel was allowed to cool over a period of 1~ hours, and was vented at 30C. The polymer was recovered by filtration, washed with methanol, then acetone and air dried at room temperature.
4.62g of polymer was recovered.
5--3 1 ~"; P~
Examples 2-5 Use of Anions accordin~ to the Invention The method of Example 1, except that HBSA was replaced with a mixture of the relevant substituted salicyclic acid and boric acid (2:1 molar). The results are recorded in Table 1.
Table 1 ~xample Salicyclic Wt of Wt Oe - Time Wt of Acid SAD Boric Acid bar h Polymer Derivative mg mg g . .. _ . .. ___ 2 5-Chloro 690.3 122.8 32.6 0.46 6.41 3 5-Methyl 608.9 123.0 24.7 0.36 5.89 4 4-Methyl 607.9 123.4 25.7 0.48 5.05 5-Bromo 868.7 122.8 30.5 0.80 S.27 Examples 2-5 clearly show the improved yields of polymer obtained relative to the prior art material exemplified by Example 1. --~0
Claims (8)
1. A process for preparing polyketones by polymerising a mixture of carbon monoxide and one or more olefins in the presence of a palladium catalyst characterised in that the palladium catalyst is prepared by reacting together:
(a) a source of palladium, (b) a bidentate amine, phosphine, arsine or stibine having the formula (R1)2M-R2-M(R1)2 wherein the M atoms are independently selected from nitrogen, phosphorus, arsenic or antimony, the R1 are independently alkyl, cycloalkyl or aryl groups and R2 is an alkylene group, and (c) a source of an anion having the formula:
(I) wherein R1, R2, R3 and R4 are independently selected from the group consisting of hydrogen, C1 to C6 alkyl, chlorine, bromine and iodine with the proviso that at least one of R1, R2, R3 and R4 is other than hydrogen.
(a) a source of palladium, (b) a bidentate amine, phosphine, arsine or stibine having the formula (R1)2M-R2-M(R1)2 wherein the M atoms are independently selected from nitrogen, phosphorus, arsenic or antimony, the R1 are independently alkyl, cycloalkyl or aryl groups and R2 is an alkylene group, and (c) a source of an anion having the formula:
(I) wherein R1, R2, R3 and R4 are independently selected from the group consisting of hydrogen, C1 to C6 alkyl, chlorine, bromine and iodine with the proviso that at least one of R1, R2, R3 and R4 is other than hydrogen.
2. A process as claimed in claim 1 characterised in that the anion of formula (I) is one where one of R1, R2, R3 and R4 is selected from C1 to C4 alkyl, chlorine and bromine and the others are hydrogen.
3. A process as claimed in claim 2 characterised in that the anion of formula (I) is one where R4 is selected from methyl, chlorine or bromine.
4. A process as claimed in claim 2 characterised in that the anion of formula (I) is one where R3 is methyl.
5. A process as claimed in claim 1 characterised in that the anion of formula (I) is generated from a mixture of the corresponding salicylic acid and boric acid.
6. A process as claimed in claim 5 characterised in that the anion of formula (I) is generated in situ under the reaction conditions from a 2:1 molar ratio mixture of the corresponding salicylic acid and boric acid.
7. A process as claimed in claim 1 characterised in that either ethylene or a mixture of ethylene and propylene or ethylene and butylene are employed.
8. A process as claimed in claim 1 characterised in that it is carried out in the presence of either mathanol or ethoxyathanol.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8907624.4 | 1989-04-05 | ||
| GB898907624A GB8907624D0 (en) | 1989-04-05 | 1989-04-05 | Process for preparing polyketones |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2013305A1 true CA2013305A1 (en) | 1990-10-05 |
Family
ID=10654475
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002013305A Abandoned CA2013305A1 (en) | 1989-04-05 | 1990-03-28 | Process for preparing polyketones |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5187258A (en) |
| EP (1) | EP0391579A1 (en) |
| JP (1) | JPH02286716A (en) |
| AU (1) | AU630441B2 (en) |
| CA (1) | CA2013305A1 (en) |
| DK (1) | DK84190A (en) |
| FI (1) | FI92594C (en) |
| GB (1) | GB8907624D0 (en) |
| NO (1) | NO176802C (en) |
| NZ (1) | NZ233103A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5401794A (en) | 1994-06-03 | 1995-03-28 | Shell Oil Company | Stabilized polyketone polymer compositions |
| EP0702045A3 (en) * | 1994-09-15 | 1996-07-17 | Shell Int Research | Gas phase process for the copolymerization of carbon monoxide and ethylenically unsaturated compounds |
| AU702530B2 (en) | 1994-09-22 | 1999-02-25 | Shell Internationale Research Maatschappij B.V. | Tribological arrangement |
| US5494998A (en) * | 1994-11-14 | 1996-02-27 | Akzo Nobel N.V. | Polymerization of carbon monoxide and ethylene using catalyst containing non-coordinating, non-acidic anion |
| US5703201A (en) * | 1995-10-10 | 1997-12-30 | Akzo Nobel Nv | Catalyst for polymerization of polyketone formed by treatment with carbon monoxide and olefin |
| JP3736010B2 (en) * | 1997-03-19 | 2006-01-18 | 富士ゼロックス株式会社 | Printing device and paper feeding device |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL8503395A (en) * | 1985-12-10 | 1987-07-01 | Shell Int Research | NEW CATALYST COMPOSITIONS. |
| US4806630A (en) * | 1986-12-01 | 1989-02-21 | Shell Oil Company | Catalytic polymerization of carbon monoxide and olefin, with organo nitro or organo nitrite compound additive |
| GB8723602D0 (en) * | 1987-10-08 | 1987-11-11 | British Petroleum Co Plc | Polyketones |
| GB8723603D0 (en) * | 1987-10-08 | 1987-11-11 | British Petroleum Co Plc | Polyketones |
| GB8909476D0 (en) * | 1989-04-26 | 1989-06-14 | British Petroleum Co Plc | Process for preparing polyketones |
-
1989
- 1989-04-05 GB GB898907624A patent/GB8907624D0/en active Pending
-
1990
- 1990-03-22 EP EP90303100A patent/EP0391579A1/en not_active Ceased
- 1990-03-22 US US07/497,587 patent/US5187258A/en not_active Expired - Fee Related
- 1990-03-27 NZ NZ233103A patent/NZ233103A/en unknown
- 1990-03-28 CA CA002013305A patent/CA2013305A1/en not_active Abandoned
- 1990-04-02 JP JP2085049A patent/JPH02286716A/en active Pending
- 1990-04-03 NO NO901509A patent/NO176802C/en unknown
- 1990-04-04 DK DK084190A patent/DK84190A/en not_active Application Discontinuation
- 1990-04-04 AU AU52598/90A patent/AU630441B2/en not_active Ceased
- 1990-04-05 FI FI901734A patent/FI92594C/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0391579A1 (en) | 1990-10-10 |
| NO901509D0 (en) | 1990-04-03 |
| FI901734A0 (en) | 1990-04-05 |
| GB8907624D0 (en) | 1989-05-17 |
| DK84190D0 (en) | 1990-04-04 |
| FI92594C (en) | 1994-12-12 |
| NO176802B (en) | 1995-02-20 |
| NZ233103A (en) | 1992-04-28 |
| NO176802C (en) | 1995-05-31 |
| JPH02286716A (en) | 1990-11-26 |
| AU630441B2 (en) | 1992-10-29 |
| FI92594B (en) | 1994-08-31 |
| DK84190A (en) | 1990-10-06 |
| NO901509L (en) | 1990-10-08 |
| AU5259890A (en) | 1990-10-11 |
| US5187258A (en) | 1993-02-16 |
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